Resin composition containing ethylene-vinyl alcohol copolymer

ABSTRACT

The present invention provides a resin composition containing (A) an ethylene-vinyl alcohol copolymer and (B) an unsaturated aldehyde (B), in which the content of the unsaturated aldehyde (B) with respect to the resin composition containing the ethylene-vinyl alcohol copolymer is 0.01 ppm or more and 100 ppm or less. The unsaturated aldehyde (B) is preferably crotonaldehyde, 2,4-hexadienal, 2,4,6-octatrienal or a combination thereof. In addition, it is preferred that the resin composition further contains a boron compound, and the content of the boron compound is 100 ppm or more and 5,000 ppm or less. Also, it is preferred that the resin composition further contains a conjugated polyene compound, and the content of the conjugated polyene compound is 0.01 ppm or more and 1,000 ppm or less.

This is the national stage 371 application of PCT InternationalApplication No. PCT/JP2013/059151 filed Mar. 27, 2013, which claims thebenefit of priority of JP 2012-075227 filed Mar. 28, 2012. The entirecontents of each of the above applications are hereby incorporated byreference.

TECHNICAL FIELD

The present invention relates to a resin composition containing anethylene-vinyl alcohol copolymer and an unsaturated aldehyde.

BACKGROUND ART

For forming containers, films, sheets and the like, melt molding isoften employed, in general. Therefore, resin compositions for use informing these containers and the like are desired to be capable offorming containers and the like that are superior in appearancecharacteristics without occurrences of defects such as fish eyes andstreaks, and to be superior in long-run workability not accompanied byoccurrences of the aforementioned defects even if melt molding iscarried out for a long time period, and the like. In addition, the fisheyes and the like not only deteriorate the appearance of containers andthe like, but also cause deterioration of performances; therefore, acomposition capable of suppressing these occurrences is needed.

On the other hand, ethylene-vinyl alcohol copolymers (hereinafter, maybe abbreviated as “EVOH(s)”) are polymeric materials that are superiorin barrier properties against gas such as oxygen, oil resistance,antistatic properties, mechanical strength and the like; therefore,resin compositions containing EVOH have been widely used as moldingmaterials of containers, sheets, films and the like.

However, since EVOH has a comparatively active hydroxyl group in itsmolecule, an oxidation reaction and/or a crosslinking reaction is causedin a molten state at high temperatures even in the interior of anextrusion molding machine in a state being almost free from oxygen, andthus thermal deterioration products may be generated. Particularly, whena continuous operation is carried out for a long period of time, thethermal deterioration products are deposited in the molding machine togenerate gels and seeds (i.e., dirt under paint) that account for fisheyes, thereby leading to a disadvantage that the resin compositioncontaining EVOH has insufficient long-run workability.

In order to ameliorate the disadvantages described above, a variety ofresin compositions containing EVOH have been developed. For example, aresin composition containing EVOH having improved long-run workabilityin melt molding by containing a boron compound, sodium acetate andmagnesium acetate (see Japanese Unexamined Patent Application,Publication No. H11-60874), a resin composition containing EVOH thatenables generation of gels and seeds by melt molding to be suppressed bycontaining a conjugated polyene compound (see Japanese Unexamined PatentApplication, Publication No. H9-71620), a resin composition containingEVOH that is superior in thermal stability and is accompanied bysuppressed formation of oxidized gels at high temperatures, due tocontaining a specific carboxylic acid metal salt and a hindered phenolantioxidant (see Japanese Unexamined Patent Application, Publication No.H4-227744), and the like have been developed.

However, long-run workability of these conventional resin compositionscontaining EVOH is not considered to be sufficient, and in a case wherea metal salt is contained in the composition in a large amount,yellowing of the resulting molded articles such as containers occurs,leading to a disadvantage of being likely to have unfavorableappearances.

In addition, a production method of EVOH has been known in whichcrotonaldehyde is coexisted in a polymerization step of ethylene andvinyl acetate (see Japanese Unexamined Patent Application, PublicationNo. 2007-31725). According to this production method, an adhesion ofscales in the interior of a polymerization tank can be suppressed by thecoexistence of crotonaldehyde during polymerization. As a result, inregard to films of EVOH produced by this production method, generationof fish eyes resulting from the scales detached and contaminated in thepolymer can be reportedly decreased.

However, in the production method, crotonaldehyde added in thepolymerization is consumed in the polymerization step and asaponification step, and further washed away with water in a washingstep and the like; therefore, crotonaldehyde hardly remains in a finallyobtained resin composition containing EVOH since the solubility ofcrotonaldehyde in water is 18.1 g/100 g at 20° C. (see THE MERCK INDEX14th 2006). Therefore, effects of the unsaturated aldehyde such ascrotonaldehyde on an improvement of thermal stability and/or long-runworkability in a secondary processing (melt molding, etc.) of theresultant EVOH has been unknown.

To provide a multilayered structure that is superior in the appearancethrough suppressing generation of gels, fish eyes and the like byimproving thermal stability of EVOH has been known (see JapaneseUnexamined Patent Application, Publication No. 2001-72823). However, inrecent tide of environmental handling such as a reduction in amounts ofpackaging materials and a reduction in amounts of waste, a reduction inthicknesses of cups, bottles, films and the like has been desired, andthere arises needs for additional improvements of the appearances, whichhave not mattered on conventional packaging materials.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Unexamined Patent Application, PublicationNo. H11-60874

Patent Document 2: Japanese Unexamined Patent Application, PublicationNo. H9-71620

Patent Document 3: Japanese Unexamined Patent Application, PublicationNo. H4-227744

Patent Document 4: Japanese Unexamined Patent Application, PublicationNo. 2007-31725

Patent Document 5: Japanese Unexamined Patent Application, PublicationNo. 2001-72823

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

The present invention was made in view of the foregoing circumstances,and an object of the invention is to provide a resin composition beingcapable of forming molded articles that are superior in appearancecharacteristics with suppressed occurrences of defects such as fisheyes, streaks, etc., which result from melt molding, and also beingsuperior in long-run workability even if used in melt molding inparticular. Further a production method of such a resin composition isprovided according to the present invention.

Means for Solving the Problems

According to an aspect of the invention made for solving theaforementioned problems, a resin composition contains (A) anethylene-vinyl alcohol copolymer and (B) an unsaturated aldehyde, inwhich the content of the unsaturated aldehyde (B) with respect to theresin composition containing the ethylene-vinyl alcohol copolymer is0.01 ppm or more and 100 ppm or less.

Due to containing the EVOH (A) and the specific amount of theunsaturated aldehyde (B), the resin composition according to the aspectof the present invention leads to suppression of occurrences of defectssuch as fish eyes, gels and streaks which result from melt molding;therefore, molded articles formed therefrom can be superior inappearance characteristics. In addition, even if the resin compositionis subjected to melt molding for a long time period in particular, thedefects are less likely to occur, and sufficient long-run workability isattained.

The unsaturated aldehyde (B) is preferably (B-1) an unsaturatedaliphatic aldehyde, and more preferably at least one selected from thegroup consisting of crotonaldehyde, 2,4-hexadienal and2,4,6-octatrienal.

The action of the unsaturated aldehyde (B) in suppressing the generationof the fish eyes, gels, streaks and the like which result from meltmolding is not necessarily clear. However, since the unsaturatedaldehyde (B) is more likely to be oxidized as compared with EVOH (A),generation of fish eyes as well as gels, streaks and the like presumedto occur through oxidative degradation of EVOH (A) by heat melting issupposed to be suppressed owing to the unsaturated aldehyde (B) morerapidly oxidized than EVOH (A).

It is preferred that a boron compound is further contained, and thecontent of the boron compound is 100 ppm or more and 5,000 ppm or less.

When the resin composition further contains the specific amount of theboron compound, it becomes difficult to cause gelation in melt molding,and suppression of a torque fluctuation of an extrusion molding machineor the like is enabled. Accordingly, the resin composition can formmolded articles such as containers that are superior in appearancecharacteristics, and long-run workability can be improved. It is to benoted that the content of the boron compound herein is a value derivedin terms of boric acid equivalent.

It is preferred that a conjugated polyene compound is further contained,and the content of the conjugated polyene compound is 0.01 ppm or moreand 1,000 ppm or less.

When the resin composition further contains the specific amount of theconjugated polyene compound, oxidative degradation in melt molding canbe suppressed. Accordingly, the resin composition can further suppressthe occurrences of defects such as fish eyes, and coloring, wherebymolded articles such as containers which are more superior in theappearance characteristics can be formed, and also the long-runworkability can be improved.

It is preferred that the conjugated polyene compound is sorbic acidand/or a sorbic acid salt. When the resin composition contains sorbicacid and/or the sorbic acid salt as the conjugated polyene compound,oxidative degradation in melt molding can be more effectivelysuppressed. Accordingly, the resin composition can further suppress theoccurrences of defects such as fish eyes, and coloring, thereby enablingthe appearance characteristics of the molded articles formed therefromto be improved, and more superior long-run workability is attained.

It is preferred that acetic acid and/or an acetic acid salt are/isfurther contained, and the content of acetic acid and/or the acetic acidsalt is 50 ppm or more and 1,000 ppm or less. When the resin compositionfurther contains the specific amount of acetic acid and/or the aceticacid salt, coloring of the molded articles formed therefrom can beprevented. It is to be noted that the content of acetic acid and/or theacetic acid salt herein is a value derived in terms of acetic acidequivalent.

It is preferred that a phosphorus compound is further contained, and thecontent of the phosphorus compound is 1 ppm or more and 200 ppm or less.When the resin composition further contains the specific amount of thephosphorus compound, occurrences of defects such as fish eyes, andcoloring can be further suppressed, whereby the appearancecharacteristics of the molded articles formed therefrom can be furtherimproved, and also still superior long-run workability can be attained.It is to be noted that the content of the phosphorus compound herein isa value derived in terms of phosphorus element equivalent.

According to another aspect of the present invention, a multilayeredstructure is provided which includes at least one or more layers eachconstituted with the resin composition. When the resin composition isused, in the case of a continuous operation for a long time period,retention and adhesion of a deteriorated resin inside/outside a dieresulting from thermal deterioration can be prevented. Thus, amultilayered structure having a favorable appearance can be obtainedeven when a continuous operation is carried out for a long time period.

Effects of the Invention

Since the resin composition according to the aspect of the presentinvention enables the occurrences of defects such as fish eyes, gels andstreaks in melt molding to be suppressed, molded articles such ascontainers and films which are superior in appearance characteristicscan be formed. In addition, according to the resin composition and themultilayered structure, the defects are less likely to occur even ifmelt molding is carried out for a long time period in particular, andalso superior long-run workability is attained. Therefore, the resincomposition can be suitably used as various types of packaging materialsthrough molding into containers, films, sheets and the like.

DESCRIPTION OF EMBODIMENTS

Hereinafter, preferred embodiments for carrying out the presentinvention will be explained, but the present invention is not limitedthereto. Moreover, unless stated particularly, materials illustrated maybe used either alone, or two or more types thereof may be used incombination.

Resin Composition

The resin composition according to an embodiment of the presentinvention contains (A) EVOH and (B) an unsaturated aldehyde, and thecontent of the unsaturated aldehyde (B) with respect to the resincomposition containing the ethylene-vinyl alcohol copolymer is 0.01 ppmor more and 100 ppm or less. Furthermore, the resin composition containsa boron compound, a conjugated polyene compound, a phosphorus compound,and acetic acid and/or an acetic acid salt as suitable components. Also,the resin composition may contain other optional component(s) except forthese components, within a range not leading to impairment of theeffects of the present invention. The EVOH (A), the unsaturated aldehyde(B), the boron compound, the conjugated polyene compound, acetic acidand/or the acetic acid salt, the phosphorus compound, and the otheroptional component(s) will be described in detail below.

EVOH (A)

EVOH (A) used in the embodiment of the present invention is anethylene-vinyl alcohol copolymer obtained by saponifying anethylene-vinyl ester copolymer.

The EVOH (A) has an ethylene content of typically 20 mol % or more and60 mol % or less, preferably 24 mol % or more and 55 mol % or less, morepreferably 27 mol % or more and 45 mol % or less, still more preferably27 mol % or more and 42 mol % or less, and even more preferably 27 mol %or more and 38 mol % or less. When the ethylene content is less than 20mol %, gelation of the resin composition becomes likely to occur due todecreased thermal stability in melt extrusion, and thus defects such asstreaks and fish eyes are likely to occur. In particular, when theoperation is carried out for a long time period under conditionsinvolving a higher temperature or higher speed than that in conditionsfor general melt extrusion, gelation of the resin composition becomesremarkable. Moreover, when the resin composition has an ethylene contentof greater than mol %, gas barrier properties are impaired and intrinsiccharacteristics of the EVOH may not be maintained.

The degree of saponification of a vinyl ester component of the EVOH (A)is typically 85% or more, preferably 90% or more, more preferably 98% ormore, and still more preferably 99% or more. When the degree ofsaponification of the vinyl ester component of the EVOH (A) in the resincomposition is less than 85%, thermal stability may be insufficient.

A typical vinyl ester used for producing the EVOH (A) is exemplified byvinyl acetate; however, in addition thereto, other fatty acid vinylester such as vinyl propionate and vinyl pivalate may be used.

In addition to the ethylene and the vinyl ester, a vinylsilane compoundmay be further used as a copolymer component for the EVOH (A). Thecontent of the vinylsilane compound in the EVOH (A) is 0.0002 to 0.2 mol%.

Examples of the vinylsilane compound include vinyltrimethoxysilane,vinyltriethoxysilane, vinyltri(β-methoxy-ethoxy) silane,γ-methacryloxypropylmethoxysilane, and the like. Of these,vinyltrimethoxysilane and vinyltriethoxysilane are preferred.

For the EVOH (A), other monomer (s) except for ethylene, vinyl estersand vinylsilane compounds may be used as a copolymer component, within arange not leading to impairment of the effects of the present invention.

Examples of the other monomer include:

unsaturated hydrocarbons such as propylene and butylene;

unsaturated carboxylic acids or esters thereof such as (meth)acrylicacid, methyl(meth)acrylate and ethyl(meth)acrylate;

vinylpyrrolidones such as N-vinylpyrrolidone, and the like.

The content of the EVOH (A) in the resin composition is typically 95% bymass or more, preferably 98.0% by mass or more, more preferably 99.0% bymass or more, and still more preferably 99.5% by mass or more. When thecontent of the EVOH (A) falls within the above-specified range, themolded articles obtained from the resin composition have superiorbarrier properties against various types of gases, oil resistance, andthe like.

Unsaturated Aldehyde (B)

The resin composition according to the embodiment of the presentinvention contains in addition to the EVOH (A), 0.01 ppm or more and 100ppm or less of the unsaturated aldehyde (B) as an essential component.Due to containing the specific amount of the unsaturated aldehyde (B),the resin composition can suppress the occurrences of defects such asfish eyes, gels and streaks which result from melt molding; therefore,the molded articles formed therefrom can be superior in appearancecharacteristics. In addition, even if the resin composition is subjectedto melt molding for a long time period in particular, the defects areless likely to occur, and thus superior long-run workability isattained. In addition, as a consequence of containing such anunsaturated aldehyde (B), the amount of other components such as theconjugated polyene compound added for the purpose of achieving similareffects can be decreased, and superior long-run workability can beattained in an entirely small amount of addition.

The unsaturated aldehyde (B) is an aldehyde having a carbon-carbondouble bond or triple bond in its molecule, and is preferably anunsaturated aliphatic aldehyde (B-1) and more preferably at least oneselected from the group consisting of crotonaldehyde, 2,4-hexadienal and2,4,6-octatrienal.

The content of the unsaturated aldehyde (B) with respect to the resincomposition is 0.01 ppm or more and 100 ppm or less, preferably 0.05 ppmor more and 50 ppm or less, more preferably 0.1 ppm or more and 30 ppmor less, and still more preferably 0.2 ppm or more and 5 ppm or less.When the content of the unsaturated aldehyde (B) in the resincomposition is less than 0.01 ppm, long-run workability in melt moldingmay be insufficient, and occurrences of defects such as fish eyes, gelsand streaks over time cannot be suppressed. In addition, when thecontent of the unsaturated aldehyde (B) is greater than 100 ppm, acrosslinking effect is exhibited in melt molding through condensation ofthe unsaturated aldehyde (B) as well as a reaction between the EVOH (A)and a condensate of the unsaturated aldehyde (B), thereby leading to anincrease in the viscosity or gelation such that occurrences of defectssuch as gels, seeds and streaks may be caused, and coloring of the resincomposition becomes more likely to occur. The content of the unsaturatedaldehyde (B) in the resin composition as referred to herein isrepresented by a proportion with respect to the total mass of the solidcontent of the resin composition, and specifically, is a value obtainedby a quantitative determination of the unsaturated aldehyde (B)contained in the resin composition dried.

The unsaturated aldehyde (B) is preferably (B-1) an unsaturatedaliphatic aldehyde, more preferably an aldehyde having a carbon-carbondouble bond in its molecule such as acrylaldehyde (acrolein),crotonaldehyde, methacrylaldehyde, 2-methyl-2-butenal, 2-butynal,2-hexenal, 2,6-nonadienal, 2,4-hexadienal, 2,4,6-octatrienal, 2-hexenaland 5-methyl-2-hexenal, as well as an aldehyde having a carbon-carbontriple bond such as propiolaldehyde, 2-butyn-1-al and 2-pentyn-1-al,still more preferably a linear or branched unsaturated aliphaticaldehyde having a carbon-carbon double bond, even more preferably atleast one selected from the group consisting of crotonaldehyde,2,4-hexadienal and 2,4,6-octatrienal. In particular, crotonaldehydehaving a boiling point of about 100° C. and having a high solubility inwater is further preferred because of ease in eliminating an excess, oradding a shortage as needed in a washing step and/or a drying step, forexample. The unsaturated aldehyde (B) has preferably 3 to 10 carbonatoms, more preferably 4 to 8 carbon atoms, and still more preferably 4,6 or 8 carbon atoms, including aldehyde moieties.

Boron Compound

It is preferred that the resin composition further contains 100 ppm ormore and 5,000 ppm or less of a boron compound. When the resincomposition contains the boron compound in the specific amount, gelationis less likely to occur in melt molding, and a torque fluctuation of anextrusion molding machine and the like can be suppressed. Accordingly,the resin composition can form a container and the like being superiorin appearance characteristics, and the long-run workability can beimproved. It is to be noted that the content of the boron compound is avalue derived in terms of boric acid equivalent.

Examples of the boron compound include:

boric acids such as orthoboric acid, metaboric acid and tetraboric acid;

boric acid esters such as triethyl borate and trimethyl borate;

boric acid salts such as alkali metal salts or alkaline earth metalsalts of the aforementioned boric acids, and borax;

boron hydrides, and the like. Of these, boric acids are preferred, andorthoboric acid (hereinafter, may be also merely referred to as “boricacid”) is more preferred.

The content of the boron compound is 100 ppm or more and 5,000 ppm orless, preferably 100 ppm or more and 4,000 ppm or less, and morepreferably 150 ppm or more and 3,000 ppm or less. When the resincomposition has the content of the boron compound falling within theabove-specified range, a torque fluctuation of an extrusion moldingmachine and the like in heat melting can be effectively suppressed. Whenthe content of the boron compound of the resin composition is less than100 ppm, the effects cannot be sufficiently exhibited, whereas when thecontent is greater than 5,000 ppm, appearance characteristics of themolded articles formed therefrom may be insufficient since gelation islikely to occur.

Conjugated Polyene Compound

It is preferred that the resin composition further contains 0.01 ppm ormore and 1,000 ppm or less of a conjugated polyene compound. When theresin composition further contains the specific amount of the conjugatedpolyene compound, oxidative degradation in melt molding can besuppressed. Accordingly, the resin composition further suppressesoccurrences of defects such as fish eyes, and coloring, leading to animprovement of the appearance characteristics of the molded articlesformed therefrom, and also further superior long-run workability isachieved.

The conjugated polyene compound as referred to means a compound having aconjugated double bond, as generally referred to, i.e., a compound:having a structure formed by alternately linking a carbon-carbon doublebond and a carbon-carbon single bond; and having two or morecarbon-carbon double bonds. The conjugated polyene compound may be aconjugated diene having two double bonds, a conjugated triene havingthree double bonds, or a conjugated polyene having more than threeconjugated double bonds. In addition, the conjugated double bond may bepresent in a multiple number in a single molecule without beingconjugated one another. For example, compounds having three conjugatedtriene structures in the same molecule, such as tung oil, may be alsoincluded in the conjugated polyene compound.

The conjugated polyene compound preferably has 7 or less conjugateddouble bonds. When the resin composition contains a conjugated polyenecompound having 8 or more conjugated double bonds, coloring of themolded articles formed therefrom is likely to occur.

The conjugated polyene compound may have in addition to the conjugateddouble bond, other functional group such as a carboxyl group and a saltthereof, a hydroxyl group, an ester group, a carbonyl group, an ethergroup, an amino group, an imino group, an amide group, a cyano group, adiazo group, a nitro group, a sulfone group and a salt thereof, asulfonyl group, a sulfoxide group, a sulfide group, a thiol group, aphosphoric acid group and a salt thereof, a phenyl group, a halogenatom, a double bond, and a triple bond.

Examples of the conjugated polyene compound include:

conjugated diene compounds such as isoprene, 2,3-dimethyl-1,3-butadiene,2,3-diethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene,3,4-dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene,2,5-dimethyl-2,4-hexadiene, 1,3-octadiene, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1-phenyl-1,3-butadiene, 1,4-diphenyl-1,3-butadiene,1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene,1-ethoxy-1,3-butadiene, 2-ethoxy-1,3-butadiene, 2-nitro-1,3-butadiene,chloroprene, 1-chloro-1,3-butadiene, 1-bromo-1,3-butadiene,2-bromo-1,3-butadiene, ocimene, phellandrene, myrcene, farnesene,cembrene, sorbic acid, sorbic acid esters, sorbic acid salts and abieticacid;

conjugated triene compounds such as 1,3,5-hexatriene,2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil,cholecalciferol, fulvene and tropone;

conjugated polyene compounds such as cyclooctatetraene,2,4,6,8-decatetraene-1-carboxylic acid, retinol and retinoic acid; andthe like. The aforementioned conjugated polyene compound may be usedalone, or two or more types thereof be used in combination.

The conjugated polyene compound has preferably 4 to 30 carbon atoms, andmore preferably 4 to 10 carbon atoms.

Among these, sorbic acid, a sorbic acid ester, a sorbic acid salt,myrcene and an arbitrary mixture of these are preferred, and sorbicacid, a sorbic acid salt and a mixture of these are more preferred.Sorbic acid, a sorbic acid salt and a mixture of these exhibit superiorsuppressive effects on oxidative degradation at high temperatures, andare preferred also in light of hygienic properties and availabilitysince they are industrially used broadly also as food additives.

The molecular weight of the conjugated polyene compound is typically1,000 or less, preferably 500 or less, and more preferably 300 or less.When the molecular weight of the conjugated polyene compound is greaterthan 1,000, the state of dispersion in EVOH (A) may be inferior, andthus the appearance after the melt molding may be unfavorable.

The content of the conjugated polyene compound is 0.01 ppm or more and1,000 ppm or less, preferably 0.1 ppm or more and 1,000 ppm or less,more preferably 0.5 ppm or more and 800 ppm or less, and still morepreferably 1 ppm or more and 500 ppm or less. When the content of theconjugated polyene compound in the resin composition is less than 0.01ppm, the effect of suppressing oxidative degradation in melt molding maynot be satisfactorily achieved. On the other hand, when the content isgreater than 1,000 ppm, gelation of the resin composition isaccelerated, and thus the appearance of the molded articles formedtherefrom is likely to be unfavorable.

Japanese Unexamined Patent Application, Publication No. H9-71620discloses that a resin composition accompanied by less generation ofgelatinous seeds in molding can be obtained by adding a conjugatedpolyene compound in a step after the polymerization. However, accordingto the present invention, it was newly found that by further adding theunsaturated aldehyde (B) in addition to the conjugated polyene compound,occurrences of defects such as fish eyes, and coloring can be furthersuppressed, whereby the appearance characteristics of the moldedarticles formed therefrom can be improved, and additionally, the resincomposition that is superior also in long-run workability can beobtained.

Acetic Acid and/or Acetic Acid Salt

The resin composition preferably contains 50 ppm or more and 1,000 ppmor less of acetic acid and/or an acetic acid salt (i.e., acetic acid, anacetic acid salt or a combination thereof). When the resin compositionfurther contains the specific amount of acetic acid and/or the aceticacid salt, coloring of the molded articles formed therefrom can beprevented. It is to be noted that the content of acetic acid and/or theacetic acid salt is a value derived in terms of acetic acid equivalent.

As acetic acid and/or the acetic acid salt, both acetic acid and theacetic acid salt are preferably used, and acetic acid and sodium acetateare more preferably used.

The content of acetic acid and/or the acetic acid salt is preferably 50ppm or more and 1,000 ppm or less, more preferably 100 ppm or more and1,000 ppm or less, still more preferably 150 ppm or more and 500 ppm orless, and particularly preferably 200 ppm or more and 400 ppm or less.When the content of acetic acid and/or the acetic acid salt is less than50 ppm, a sufficient preventive effect on coloring cannot be achieved;therefore, yellowing of the molded articles formed from the resincomposition may be found. When the content of acetic acid and/or theacetic acid salt in the resin composition is greater than 1,000 ppm,gelation is likely to occur in melt molding, particularly in meltmolding over a long time period, and thus the appearance of the moldedarticles may be unfavorable.

Phosphorus Compound

The resin composition preferably contains 1 ppm or more and 200 ppm orless of a phosphorus compound. When the resin composition furthercontains the specific amount of the phosphorus compound, occurrences ofdefects such as fish eyes, and coloring can be further suppressed, andthus the appearance characteristics of the molded articles formedtherefrom can be improved, with further superior long-run workabilityattained. It is to be noted that the content of the phosphorus compoundis a value derived in terms of phosphorus element equivalent.

Examples of the phosphorus compound include various types of phosphoricacids such as phosphoric acid and phosphorous acid, phosphate, and thelike.

The phosphate may be in any form of a monobasic phosphate salt, adibasic phosphate salt and a tribasic phosphate salt. In addition, thecationic species contained in the phosphate is not particularly limited,and an alkali metal salt, and an alkaline earth metal salt arepreferred. Of these, sodium dihydrogen phosphate, potassium dihydrogenphosphate, disodium hydrogen phosphate and dipotassium hydrogenphosphate are more preferred, and sodium dihydrogen phosphate anddipotassium hydrogen phosphate are even more preferred.

The content of the phosphorus compound in the resin composition ispreferably 1 ppm or more and 200 ppm or less, more preferably 2 ppm ormore and 150 ppm or less, still more preferably 3 ppm or more and 150ppm or less, and particularly preferably 5 ppm or more and 100 ppm orless. When the content of the phosphorus compound in the resincomposition is less than 1 ppm, or is greater than 200 ppm, thermalstability is deteriorated, and thus disadvantages of generation ofgelatinous seeds, and coloring in the melt molding over a long timeperiod are likely to be caused.

Other Optional Components

The resin composition may contain an alkali metal as other optionalcomponent, within a range not leading to impairment of the effects ofthe present invention. Examples of the alkali metal include lithium,sodium, potassium and the like. Moreover, the alkali metal may becontained in the form of an alkali metal salt. Examples of the alkalimetal salt include aliphatic carboxylic acid salts and aromaticcarboxylic acid salts with a monovalent metal, metal complexes, and thelike. Specific examples of the alkali metal salt include sodium acetate,potassium acetate, sodium stearate, potassium stearate, sodium salts ofethylenediamine tetraacetate, and the like. Of these, sodium acetate andpotassium acetate are preferred. The content of the alkali metal in theresin composition is preferably 20 to 1,000 ppm, and more preferably 50to 500 ppm.

The resin composition may contain an antioxidant, an UV absorbent, aplasticizer, an antistatic agent, a lubricant, a colorant, a filler, aheat stabilizer, an other resin, a metal salt of a higher aliphaticcarboxylic acid, a hydrotalcite compound and the like as other optionalcomponents, as well as the aforementioned alkali metal. The resincomposition may contain one, or two or more types of these optionalcomponents, and the content of the optional component(s) is 1% by massor less in total.

Examples of the antioxidant include 2,5-di-t-butylhydroquinone,2,6-di-t-butyl-p-cresol, 4,4′-thiobis-(6-t-butylphenol),2,2′-methylene-bis-(4-methyl-6-t-butylphenol), octadecyl3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate,4,4′-thiobis-(6-t-butylphenol), and the like.

Examples of the UV absorbent include ethylene2-cyano-3,3′-diphenylacrylate,2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone,2-hydroxy-4-octoxybenzophenone.

Examples of the plasticizer include dimethyl phthalate, diethylphthalate, dioctyl phthalate, waxes, liquid paraffins, phosphoric acidesters, and the like.

Examples of the antistatic agent include pentaerythritol monostearate,sorbitan monopalmitate, sulfated polyolefins, polyethylene oxides,CARBOWAX (trade name), and the like.

Examples of the lubricant include ethylene bisstearamide, butylstearate, and the like.

Examples of the colorant include carbon black, phthalocyanine,quinacridone, indoline, azo pigment, colcothar, and the like.

Examples of the filler include glass fibers, wollastonite, calciumsilicate, talc, montmorillonite, and the like.

Examples of the heat stabilizer include hindered phenol compounds,hindered amine compounds, and the like.

Examples of the other resin include polyamides, polyolefins, and thelike.

Examples of the metal salt of a higher aliphatic carboxylic acid includecalcium stearate, magnesium stearate, and the like.

In order to prevent generation of gels, one, or two or more types of thehydrotalcite compound, the hindered phenol heat stabilizer, the hinderedamine heat stabilizer and the metal salt of a higher aliphaticcarboxylic acid may be added in an amount of 0.01 to 1% by mass.

Production Method of Resin Composition

The production method of the resin composition according to theembodiment of the present invention is not particularly limited as longas the unsaturated aldehyde (B) can be homogenously blended in EVOH (A),and the unsaturated aldehyde (B) in an amount falling within the rangeof 0.01 ppm or more and 100 ppm or less can be contained in the resincomposition finally obtained.

However, the production method according to the embodiment of thepresent invention is preferably a production method of a resincomposition containing the ethylene-vinyl alcohol copolymer includingthe steps of:

(1) copolymerizing ethylene with a vinyl ester; and

(2) saponifying a polymer obtained in the step (1), in which

0.01 ppm or more and 100 ppm or less of the unsaturated aldehyde (B) iscontained in the resin composition.

The procedure for allowing the specific amount of the unsaturatedaldehyde (B) to be contained in the resin composition is notparticularly limited, but the procedure may be exemplified by:

adding the specific amount of the unsaturated aldehyde (B) in the step(1);

adding the specific amount of the unsaturated aldehyde (B) in the step(2);

adding the specific amount of the unsaturated aldehyde (B) to the EVOH(A) obtained in the step (2), and the like.

However, when the procedure of adding the specific amount of theunsaturated aldehyde (B) in the step (1), or the procedure of adding thespecific amount of the unsaturated aldehyde (B) in the step (2) isemployed, in order to allow a desired amount of the unsaturated aldehyde(B) to be contained in the resulting resin composition, it is necessaryto increase the amount of addition taking into consideration the amountconsumed by a polymerization reaction in the step (1) and/or by asaponification reaction in the step (2). Whereas, in the case in whichthe amount of the unsaturated aldehyde (B) is too large, these reactionsmay be inhibited. In addition, since the amount consumed by thepolymerization reaction and/or the saponification reaction may varydepending on the reaction conditions, it would be difficult to regulatethe content of the unsaturated aldehyde (B) in the resin composition.Therefore, the procedure of adding, after the step (2), the specificamount of the unsaturated aldehyde (B) to the EVOH (A) obtained in thestep (2) is preferred.

The procedure for adding the specific amount of the unsaturated aldehyde(B) to the EVOH (A) may be exemplified by:

pelletizing after blending the unsaturated aldehyde (B) with EVOH (A)beforehand to give pellets;

impregnating a strand obtained by deposition of a paste aftersaponification of the ethylene-vinyl ester copolymer with theunsaturated aldehyde (B);

impregnating the strand obtained by deposition after cutting, with theunsaturated aldehyde (B);

adding the unsaturated aldehyde (B) to a solution of redissolved chipsof a dry resin composition;

melt kneading a blend of two components of the EVOH (A) and theunsaturated aldehyde (B);

feeding the unsaturated aldehyde (B) to be contained in a melt of theEVOH (A) during extrusion;

producing a masterbatch by blending a high concentration of theunsaturated aldehyde (B) with a part of the EVOH (A) and pelletizing theblend, and dry blending the masterbatch with the EVOH (A) and the meltkneading the mixture; or the like.

Of these, in light of a possibility of homogenously dispersing a slightamount of the unsaturated aldehyde (B) in the EVOH (A), pelletizingafter blending the unsaturated aldehyde (B) with EVOH (A) beforehand togive pellets is preferred for the procedure of mixing the unsaturatedaldehyde (B). Specifically, the unsaturated aldehyde (B) is added to asolution prepared by dissolving the EVOH (A) in a good solvent such as amixed solvent of water and methanol, and thus resulting mixture solutionis extruded into a poor solvent through a nozzle or the like to allowfor deposition and/or coagulation, followed by washing and/or drying thesame, whereby the pellets including the unsaturated aldehyde (B)homogenously mixed with the EVOH (A) can be obtained.

Also, in pelletizing to give the pellets, the conjugated polyenecompound may be added together with the unsaturated aldehyde (B). Byadding the unsaturated aldehyde (B) and the conjugated polyene compound,the occurrences of defects such as fish eyes, and coloring can befurther suppressed, and thus the appearance characteristics of themolded articles formed therefrom can be improved. In addition, the resincomposition that is also superior in long-run workability can beobtained.

The procedure for allowing each component other than the unsaturatedaldehyde (B) to be contained in the resin composition may be exemplifiedby:

mixing the pellets with each component, followed by melt kneading;

mixing each component together with the unsaturated aldehyde (B) inpreparing the pellets;

immersing the pellets in a solution containing each component; and thelike. Note that a ribbon blender, a high speed mixer, a cokneader, amixing roll, an extruder, an intensive mixer and the like may beemployed for the mixing.

Production Method of Molded Article

The resin composition may be used to produce molded articles having asingle-layer structure, or together with any of other various types ofbase materials, molded articles having a multilayer structure includingtwo or more types of layers.

When a molded article having a multilayer structure is produced, athermoplastic resin layer may be situated adjacent to a layerconstituted with the resin composition.

Examples of preferred resins for forming the thermoplastic resin layerinclude:

polyethylenes having a high density, medium density or low density;

polyethylenes prepared by copolymerizing vinyl acetate, an acrylic acidester, or an α-olefin such as butene or hexene with ethylene;

ionomer resins;

polypropylene homopolymers;

polypropylenes prepared by copolymerizing an α-olefin such as ethylene,butene or hexane with propylene;

polyolefins such as modified polypropylene to which a rubber polymer wasblended;

resins obtained by addition or grafting of maleic anhydride to theseresins.

The molded article of the multilayer structure may further have athermoplastic resin layer other than those described above, and theresin for forming the thermoplastic resin layer is preferably apolyamide resin, a polyester resin, a polystyrene resin, a polyvinylchloride resin, an acrylic resin, a polyurethane resin, a polycarbonateresin, a polyvinyl acetate resin, and the like. Of these, a polyesterresin is preferred.

Although a method for obtaining the multilayered structure is notparticularly limited, examples of the method include an extrusionlamination method, a dry lamination method, an extrusion blow moldingmethod, a coextrusion lamination method, a coextrusion sheet moldingmethod, a coextrusion pipe molding method, a coextrusion blow moldingmethod, a coinjection molding method, a solution coating method, and thelike. It is to be noted that the laminate having a multilayer structureobtained by such a method may be further subjected to a secondaryprocessing by a method such as deep-draw vacuum molding or blow moldingafter reheating at a temperature falling within the range of notexceeding the melting point of the EVOH (A).

Note that scraps generated in carrying out the extrusion molding, blowmolding, heat molding and the like may be reused through blending in thethermoplastic resin layer, or may be separately used as a recoverylayer.

Although the layer structure of the multilayered structure is notparticularly limited, in light of moldability, cost and the like,examples of a typical layer structure include those having layers of: athermoplastic resin/the resin composition/a thermoplastic resin; theresin composition/an adhesive resin/a thermoplastic resin; and athermoplastic resin/an adhesive resin/the resin composition/an adhesiveresin/a thermoplastic resin in these orders. Of these, the layerstructure having layers of a thermoplastic resin/the resin composition/athermoplastic resin in this order is preferred. More specifically, thelayer structure having layers constituted with a thermoplastic polyesterresin directly laminated on two sides of the layer constituted with theresin composition, respectively, is more preferred. In the case in whichthe thermoplastic resin layers are provided on two outer sides of theresin composition layer, respectively, the thermoplastic resin layersprovided as two outer layers may be constituted with resins differentfrom each other, or may be constituted with an identical resin.

The multilayered structure obtained by the melt molding and the like maybe subjected to secondary processing molding such as bending processing,vacuum molding, blow molding and press molding as needed, to give amolded product as intended.

EXAMPLES

Hereinafter, the present invention is specifically explained by way ofExamples, but the present invention is not in anyhow limited to theseExamples. It is to be noted that each quantitative determination inthese Examples was carried out using the following method.

Ethylene Content and Degree of Saponification of EVOH (A)

A ¹H-NMR spectrometer (manufactured by JEOL, Ltd., “model JNM-GX-500”)was employed for the determination using DMSO-d₆ as a solvent.

Quantitative Determination of Unsaturated Aldehyde (B)

A DNPH (2,4-dinitrophenylhydrazine) preparation was prepared by adding50 mL of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), 11.5 mL of aceticacid and 8 mL of ion exchanged water to 200 mg of a 50% by mass DNPHsolution. Thereafter, dry resin composition pellets in an amount of 1 gwere added to 20 mL of the DNPH preparation, and dissolved with stirringat 35° C. for 1 hour. To this solution was added acetonitrile to permitprecipitation of the EVOH (A), and the resulting solution was filteredand concentrated to obtain an extracted sample. This extracted samplewas analyzed for a quantitative determination on high performance liquidchromatography. Thus, the amount of the unsaturated aldehyde (B) wasquantitatively determined. It is to be noted that upon the quantitativedetermination, a calibration curve produced using an authentic sampleobtained by allowing each unsaturated aldehyde (B) to react with theDNPH preparation was used.

Quantitative Determination of Conjugated Polyene Compound

The dry resin composition pellets were ground by freeze grinding, and 10g of a ground matter obtained by eliminating coarse particles using asieve having a nominal dimension of 0.150 mm (100 mesh, in accordancewith JIS Z8801-1 to 3) was packed into a Soxhlet extraction apparatus toexecute an extraction treatment using 100 mL of chloroform for 48 hrs.The amount of the conjugated polyene compound in this extraction liquidwas analyzed for a quantitative determination on high performance liquidchromatography. Thus, the amount of the conjugated polyene compound wasquantitatively determined. It is to be noted that upon the quantitativedetermination, a calibration curve produced using an authentic sample ofeach conjugated polyene compound was used.

Quantitative Determination of Acetic Acid and/or Acetic Acid Salt

The dry resin composition pellets were ground by freeze grinding. Thusobtained powders were sieved using a sieve having a nominal dimension of1 mm (16 mesh, in accordance with JIS Z8801-1 to 3). Ten grams of thepowders passed through the sieve and 50 mL of ion exchanged water werecharged into a 100 mL Erlenmeyer stoppered flask equipped with a coolingcondenser, and the mixture was stirred at 95° C. for 10 hrs andextracted. Thus resultant extraction liquid in a volume of 2 mL wasdiluted with 8 mL of ion exchanged water. The amount of carboxylic acidions in the extraction liquid diluted as described above wasquantitatively determined using ion chromatography (“IC7000”,manufactured by Yokogawa Electric Corporation). It is to be noted thatupon the quantitative determination, a calibration curve produced usingan aqueous acetic acid solution was used.

Quantitative Determination of Phosphoric Acid Compound and BoronCompound

The dry resin composition pellets were ground by freeze grinding. To 0.5g of thus obtained powders was added 5 mL of nitric acid, and subjectedto wet degradation by Speedwave MWS-2 (manufactured by BERGHOF Co.). Theliquid obtained after the wet degradation was diluted with ion exchangedwater to give a total liquid volume of 50 mL. The liquid diluted wasanalyzed for quantitative determinations of a phosphorus element and aboron element using an ICP emission spectrophotometer (“Optima 4300 DV”,manufactured by Perkin-Elmer Japan Co., Ltd.). The amount of thephosphoric acid compound was calculated as a value derived in terms ofphosphate radical equivalent, whereas the amount of the boron compoundwas calculated as a value derived in terms of boron element equivalent.It is to be noted that upon the quantitative determination, acalibration curve produced using each commercially available standardliquid was used.

Appearance of Solution (Transparency, Coloring Property)

The dry resin composition pellets were subjected to a heat treatment inthe air at 120° C. for 15 hrs, and 10 g of the resultant pellets wereweighed into a 300 ml Erlenmeyer flask. Thereto was added 100 ml of amixed solution of water and propanol (mass ratio: water/propanol=45/55),and the mixture was stirred at 75° C. for 3 hrs. Then, transparency andcoloring of the solution were evaluated by a visual inspection.

Motor Torque Fluctuation

The dry resin composition pellets in an amount of 60 g were kneaded in aLaboplast Mill (manufactured by Toyo Seiki Seisaku-sho, Ltd., “20R200”,twin-screw, counter rotating type) at 100 rpm and 260° C., and a timeperiod was determined which was required until the torque value reached1.5 times the torque value after 5 min from the beginning of thekneading.

Synthesis of EVOH (A) Synthesis Example 1

Using a 250 L pressure reaction chamber, polymerization for anethylene-vinyl acetate copolymer was carried out under the followingconditions.

vinyl acetate: 83.0 kg,

methanol: 26.6 kg,

feeding rate of 2,2′-azobisisobutylnitrile: 1,119.5 mL/hour,

polymerization temperature: 60° C.,

pressure of ethylene in polymerization chamber: 4.93 MPa,

polymerization time period: 5.0 hrs

The rate of polymerization of vinyl acetate in the resultant copolymerwas about 40%. After sorbic acid was added to this copolymerizationreaction liquid, the liquid was supplied to a purge tower, and afterunreacted vinyl acetate was eliminated from the top of the tower byintroducing methanol vapor from the bottom of the tower, a 41% methanolsolution of the ethylene-vinyl acetate copolymer was obtained. Thisethylene-vinyl acetate copolymer had an ethylene content of 32 mol %.This methanol solution of the ethylene-vinyl acetate copolymer wascharged into a saponification reactor, and a solution of sodiumhydroxide in methanol (80 g/L) was added so as to attain 0.4 equivalentswith respect to the vinyl ester component in the copolymer. Thereto wasadded methanol to adjust the copolymer concentration of 20%. Thetemperature of this solution was elevated to 60° C., and the reactionwas allowed while blowing nitrogen gas into the reactor for about 4 hrs.This solution was then extruded from a die plate provided with acircular opening into water to permit deposition, followed by cutting togive pellets having a diameter of about 3 mm and a length of about 5 mm.The pellets thus obtained were subjected to deliquoring using acentrifugal separator, and further an operation of the deliquoring afteradding a large amount of water was repeated.

Synthesis Example 2

Pellets were obtained by polymerizing, saponifying, pelletizing andwashing in a similar manner to Synthesis Example 1 except thatcrotonaldehyde was supplied so as to coexist at 0.5 ppm in the wholesystem during the polymerization.

Preparation of Resin Composition Examples 1 to 17, 19 to 27 andComparative Examples 1 to 2, 4 to 7

Twenty kg of the pellets obtained after deliquoring in Synthesis Example1 were placed into 180 kg of a mixed solvent of water and methanol (massratio: water/methanol=40/60), and the mixture was stirred at 60° C. for6 hrs to completely dissolve the pellets. To the solution thus obtainedwere added the unsaturated aldehyde (B) and the conjugated polyenecompound, and the mixture was further stirred for 1 hour such that theunsaturated aldehyde (B) and the conjugated polyene compound werecompletely dissolved, whereby a resin composition solution was obtained.This resin composition solution was continuously extruded from a nozzlehaving a diameter of 4 mm into a coagulation bath containing a mixtureof water and methanol (mass ratio: water/methanol=90/10) adjusted at 0°C. thereby permitting coagulation so as to give a strand form. Thisstrand was introduced into a pelletizing machine to obtain porous resincomposition chips. After the resultant porous resin composition chipswere washed with an aqueous acetic acid solution and ion exchangedwater, an immersion treatment in an aqueous solution containing aceticacid, sodium acetate, potassium dihydrogen phosphate and boric acid wascarried out. The resin composition chips were separated from the aqueoussolution for the immersion treatment, followed by deliquoring, andthereafter were dried in a hot-air dryer at 80° C. for 4 hrs and furtherat 100° C. for 16 hrs to obtain a resin composition (dry resincomposition pellets). The content of each component in the obtainedresin composition was quantitatively determined using the aforementionedquantitative determination methods. It is to be noted that the resincomposition was prepared such that the content of each component was asshown in Tables 1 and 2 by adjusting the amount of the unsaturatedaldehyde (B) added, and the concentration of each component in theaqueous solution for the immersion treatment.

Example 18

Pellets were obtained in a similar manner to Synthesis Example 1 exceptthat sorbic acid and crotonaldehyde were concomitantly added aftercompletion of the polymerization. Twenty kg of the resulting pelletswere placed into 180 kg of a mixed solvent of water and methanol (massratio: water/methanol=40/60), and the mixture was stirred at 60° C. for6 hrs to completely dissolve the pellets. To the solution thus obtainedwas added sorbic acid as the conjugated polyene compound, and themixture was further stirred for 1 hour such that sorbic acid iscompletely dissolved, whereby a resin composition solution was obtained.This resin composition solution was continuously extruded from a nozzlehaving a diameter of 4 mm into a coagulation bath containing a mixtureof water and methanol (mass ratio: water/methanol=90/10) adjusted at 0°C. thereby permitting coagulation so as to give a strand form. Thisstrand was introduced into a pelletizing machine to obtain porous resincomposition chips. After the resultant porous resin composition chipswere washed with an aqueous acetic acid solution and ion exchangedwater, an immersion treatment in an aqueous solution containing aceticacid, sodium acetate, potassium dihydrogen phosphate and boric acid wascarried out. The resin composition chips were separated from the aqueoussolution for the immersion treatment, followed by deliquoring, andthereafter were dried in a hot-air dryer at 80° C. for 4 hrs and furtherat 100° C. for 16 hrs to obtain a resin composition (dry resincomposition pellets). The content of each component in the obtainedresin composition was quantitatively determined using the aforementionedquantitative determination methods. It is to be noted that the resincomposition was prepared such that the content of each component was asshown in Tables 1 and 2 by adjusting the concentration of each componentin the aqueous solution for the immersion treatment.

Comparative Example 3

Twenty kg of the pellets obtained in Synthesis Example 2 were placedinto 180 kg of a mixed solvent of water and methanol (mass ratio:water/methanol=40/60), and the mixture was stirred at 60° C. for 6 hrsto completely dissolve the pellets. To the solution thus obtained wasadded sorbic acid as the conjugated polyene compound, and the mixturewas further stirred for 1 hour such that sorbic acid is completelydissolved, whereby a resin composition solution was obtained. This resincomposition solution was continuously extruded from a nozzle having adiameter of 4 mm into a coagulation bath containing a mixture of waterand methanol (mass ratio: water/methanol=90/10) adjusted at 0° C.thereby permitting coagulation so as to give a strand form. This strandwas introduced into a pelletizing machine to obtain porous resincomposition chips. After the resultant porous resin composition chipswere washed with an aqueous acetic acid solution and ion exchangedwater, an immersion treatment in an aqueous solution containing aceticacid, sodium acetate, potassium dihydrogen phosphate and boric acid wascarried out. The resin composition chips were separated from the aqueoussolution for the immersion treatment, followed by deliquoring, andthereafter were dried in a hot-air dryer at 80° C. for 4 hrs and furtherat 100° C. for 16 hrs to obtain a resin composition (dry resincomposition pellets). The content of each component in the obtainedresin composition was quantitatively determined using the aforementionedquantitative determination methods. It is to be noted that the resincomposition was prepared such that the content of each component was asshown in Tables 1 and 2 by adjusting the concentration of each componentin the aqueous solution for the immersion treatment. The amount ofcrotonaldehyde added as the unsaturated aldehyde (B) was less than thedetection lower limit.

Evaluations of Resin Composition

Each resin composition obtained in the above manner was evaluated as inthe following. The results of the evaluations are shown together inTables 1 and 2.

(1) Evaluation of Long-Run Workability

Using a single-screw extruder (“D2020”, manufactured by Toyo SeikiSeisaku-sho, Ltd.; D (mm)=20, L/D=20, compression ratio=2.0, screw: fullflight), a single-layer film having a thickness of 20 μm was producedfrom each dry resin composition pellets. In this procedure, eachcondition is as shown below.

extrusion temperature: 220° C.

screw rotation speed: 40 rpm

die width: 30 cm

roll drawing temperature: 80° C.

roll drawing speed: 3.1 m/min

A single-layer film was produced by a continuous operation under theconditions described above, and the number of defects of each producedfilm after 8 hrs and 15 hrs from the start of the operation was countedover the length of 17 cm of the film. The number of the defects wascounted using an apparatus for inspecting film defects (“AI-10”,manufactured by Frontier System Co., Ltd.). It is to be noted that acamera for detection in the apparatus was placed such that the lensthereof was situated with a distance of 195 mm away from the filmsurface. The long-run workability of each resin composition wasevaluated based on the number of the defects to be:

“favorable (A)” when the number was less than 50;

“somewhat favorable (B)” when the number was 50 or more and less than200; and

“unfavorable (C)” when the number was 200 or more.

(2) Evaluation of Appearance Characteristics

With respect to the produced film after 15 hrs, appearancecharacteristics (streaks and coloring) were evaluated by a visualinspection in accordance with the following evaluation criteria.

Evaluation Criteria of Streaks

“favorable (A)”: no streaks found.

“somewhat favorable (B)”: streaks found.

“unfavorable” (C)”: a large number of streaks found.

Evaluation Criteria of Coloring

“favorable (A)”: colorless

“somewhat favorable (B)”: yellowed

“unfavorable” (C)”: significantly yellowed

(3) Evaluation of Appearance of Solution (Transparency and Coloring)

With respect to the solution heated with stirring for 3 hrs,transparency and coloring of the solution were evaluated by a visualinspection in accordance with the following evaluation criteria.

Evaluation Criteria of Transparency

“favorable (A)”: transparent, suspended matter recognizable by thevisual inspection being absent.

“somewhat favorable (B)”: somewhat turbid, suspended matter recognizableby the visual inspection being present.

“unfavorable” (C)”: turbid, suspended matter being present.

Evaluation Criteria of Coloring of Solution

“favorable (A)”: colorless

“somewhat favorable (B)”: somewhat colored

“poor, unfavorable” (C)”: significantly colored

(4) Evaluation of Motor Torque Fluctuation

Alteration of the viscosity when heated was evaluated as follows. It isto be noted that the viscosity of the resin composition when heated is afactor that affects the long-run workability in secondary processing.

Evaluation Criteria of Motor Torque Fluctuation

“favorable (A)”: 60 min or more

“somewhat favorable (B)”: 40 min or more and less than 60 min

“unfavorable” (C)”: less than 40 min

TABLE 1 Conjugated Acetic Evaluations polyene acid/acetic PhosphorusLong-run Unsaturated aldehyde (B) compound acid salt compoundworkability Film Appearance of Motor content Boron compound contentcontent content after after appearance solution torque type (ppm) typecontent (ppm) type (ppm) type (ppm) type (ppm) 8 hrs 15 hrs streakcoloring transparency coloring fluctuation Example 1 crotonaldehyde 35boric acid 800 sorbic acid 200 acetic 300 potassium 120 A B A B A B Aacid dihydrogen sodium phosphate acetate Example 2 crotonaldehyde 2.9boric acid 800 sorbic acid 200 acetic 300 potassium 120 A A A A A A Aacid dihydrogen sodium phosphate acetate Example 3 crotonaldehyde 0.3boric acid 800 sorbic acid 200 acetic 300 potassium 120 A A A A A A Aacid dihydrogen sodium phosphate acetate Example 4 crotonaldehyde 0.3boric acid 10 sorbic acid 200 acetic 300 potassium 120 A B B A A A Aacid dihydrogen sodium phosphate acetate Example 5 crotonaldehyde 0.3boric acid 200 sorbic acid 200 acetic 300 potassium 120 A A A A A A Aacid dihydrogen sodium phosphate acetate Example 6 crotonaldehyde 0.3boric acid 2500 sorbic acid 200 acetic 300 potassium 120 A A A A A A Bacid dihydrogen sodium phosphate acetate Example 7 crotonaldehyde 0.3boric acid 4000 sorbic acid 200 acetic 300 potassium 120 B B B A A A Bacid dihydrogen sodium phosphate acetate Example 8 crotonaldehyde 0.3boric acid 800 sorbic acid 0.01 acetic 300 potassium 120 A B A B A B Bacid dihydrogen sodium phosphate acetate Example 9 crotonaldehyde 0.3boric acid 800 sorbic acid 2000 acetic 300 potassium 120 B B B B A B Bacid dihydrogen sodium phosphate acetate Example 10 crotonaldehyde 0.3boric acid 800 myrcene 200 acetic 300 potassium 120 A B A A A A B aciddihydrogen sodium phosphate acetate Example 11 crotonaldehyde 0.3 boricacid 800 potassium 200 acetic 300 potassium 120 A A A A A A A sorbateacid dihydrogen sodium phosphate acetate Example 12 crotonaldehyde 0.3boric acid 800 sorbic acid 200 acetic 5 potassium 120 A A A B A B B aciddihydrogen sodium phosphate acetate Example 13 crotonaldehyde 0.3 boricacid 800 sorbic acid 200 acetic 3000 potassium 120 A B B A A B B aciddihydrogen sodium phosphate acetate Example 14 crotonaldehyde 0.3 boricacid 800 sorbic acid 200 acetic 300 potassium 0.5 B B A A A B B aciddihydrogen sodium phosphate acetate Example 15 crotonaldehyde 0.3 boricacid 800 sorbic acid 200 acetic 300 potassium 500 B B B A A A B aciddihydrogen sodium phosphate acetate Example 16 crotonaldehyde 0.3 boricacid 800 sorbic acid 200 acetic 300 potassium 120 A A A A A A A aciddihydrogen sodium phosphate acetate Example 17 crotonaldehyde 0.08 boricacid 800 sorbic acid 200 acetic 300 potassium 120 A B B A A A B aciddihydrogen sodium phosphate acetate

TABLE 2 Conjugated Acetic Evaluations polyene acid/acetic PhosphorusLong-run Unsaturated aldehyde (B) compound acid salt compoundworkability Film Appearance of Motor content Boron compound contentcontent content after after appearance solution torque type (ppm) typecontent (ppm) type (ppm) type (ppm) type (ppm) 8 hrs 15 hrs streakcoloring transparency coloring fluctuation Example 18 crotonaldehyde 90boric acid 800 sorbic acid 50 acetic 300 potassium 120 A A A B A B Aacid dihydrogen sodium phosphate acetate Example 19 2,4-hexadienal 0.3boric acid 800 sorbic acid 200 acetic 1500 potassium 120 A B B B A B Bacid dihydrogen sodium phosphate acetate Example 20 2,4,6- 0.3 boricacid 800 sorbic acid 200 acetic 300 potassium 300 A B B B A B Boctatrienal acid dihydrogen sodium phosphate acetate Example 21crotonaldehyde 0.3 boric acid 200 sorbic acid 200 acetic 1200 potassium120 A A B A A B B acid dihydrogen sodium phosphate acetate Example 22crotonaldehyde 0.3 boric acid 2500 sorbic acid 200 acetic 1200 potassium120 A A B A A B B acid dihydrogen sodium phosphate acetate Example 23crotonaldehyde 0.3 boric acid 6000 sorbic acid 200 acetic 300 potassium120 B B B A B A B acid dihydrogen sodium phosphate acetate Example 24crotonaldehyde 0.3 boric acid 800 myrcene 200 acetic 300 potassium 300 AB B B A B B acid dihydrogen sodium phosphate acetate Example 25crotonaldehyde 0.3 boric acid 800 sorbic acid 200 acetic 0 potassium 120A B B B A B B acid dihydrogen sodium phosphate acetate Example 26crotonaldehyde 0.3 boric acid 800 sorbic acid 200 acetic 300 potassium 0B B B B A B B acid dihydrogen sodium phosphate acetate Example 27crotonaldehyde 0.08 boric acid 800 sorbic acid 1200 acetic 300 potassium120 A B B A A B A acid dihydrogen sodium phosphate acetate Comparativecrotonaldehyde 0.01 boric acid 800 sorbic acid 200 acetic 300 potassium300 B C C B B B B Example 1 acid dihydrogen sodium phosphate acetateComparative crotonaldehyde 95 boric acid 800 sorbic acid 200 acetic 300potassium 120 B C B C B C C Example 2 acid dihydrogen sodium phosphateacetate Comparative crotonaldehyde N.D. *1 boric acid 800 sorbic acid200 acetic 300 potassium 120 B C C B B C C Example 3 acid dihydrogensodium phosphate acetate Comparative crotonaldehyde N.D. *1 boric acid800 sorbic acid 0.01 acetic 300 potassium 120 B C C B C C C Example 4acid dihydrogen sodium phosphate acetate Comparative — N.D. *1 boricacid 6000 sorbic acid 0.01 acetic 3000 potassium 500 C C C C C C CExample 5 acid dihydrogen sodium phosphate acetate Comparativecrotonaldehyde N.D. *1 boric acid 800 sorbic acid 200 acetic 1500potassium 300 B C C C C C C Example 6 acid dihydrogen sodium phosphateacetate Comparative crotonaldehyde 500 boric acid 800 sorbic acid 1200acetic 300 potassium 120 C C C C C C C Example 7 acid dihydrogen sodiumphosphate acetate *1 N.D.: not detected, with the detection lower limitof 0.01 ppm

Production of Multilayered Structure Example 28

Using the following cast film formation equipment for four types,seven-layer coextrusion, a coextrusion film formation test whichinvolves the resin composition layer according to the embodiment of thepresent invention was carried out.

extruder (1): single screw, screw diameter 65 mm, L/D=22, for polyolefinof outer layer

extruder (2): single screw, screw diameter 40 mm, L/D=26, for polyolefin

extruder (3): single screw, screw diameter 40 mm, L/D=22, for adhesiveresin

extruder (4): single screw, screw diameter 40 mm, L/D=26, for EVOH

Polypropylene (hereinafter, may be abbreviated as “PP”) was fed into theextruder (1) and the extruder (2), a maleic anhydride-modifiedpolypropylene adhesive resin (ADMER QF-500 (trade name), manufactured byMitsui Chemicals, Inc.) was fed into the extruder (3), and the resincomposition obtained in Example 1 was fed into the extruder (4) toexecute coextrusion film formation. The extrusion temperature settingwas: 200 to 250° C. for the extruder (1); 200 to 250° C. for theextruder (2); 160 to 250° C. for the extruder (3); and 170 to 250° C.for the extruder (4), and the temperature setting of the feed block andthe die was 250° C. With respect to the constitutive structure and thethickness of the formed multilayer film, the target constitutivestructure having seven layers of four types, i.e., PP/PP/adhesiveresin/EVOH/adhesive resin/PP/PP=30/15/2.5/5/2.5/15/30 μm had a totalthickness of 100 μm.

The sheet was sampled 10 hrs after starting the film formation, and theappearance was observed. Consequently, an unfavorable appearanceresulting from the aggregation of EVOH, and flow marks resulting fromabnormal flow were scarcely found. Accordingly, a practically applicablemultilayer film was obtained.

Comparative Example 8

In a similar manner to Example except that the resin composition ofExample was replaced with the resin composition obtained in ComparativeExample 6, the sheet was sampled 10 hrs after starting the filmformation, and the appearance was observed. Consequently, a multilayerfilm having an unfavorable appearance resulting from the aggregation ofEVOH, and many flow marks resulting from abnormal flow was obtained.

As shown in Table 1, the resin composition according to the embodimentof the present invention is less likely to cause generation of streaks,and coloring of the molded articles formed therefrom, and a film that issuperior in appearance characteristics was successfully formed. Inaddition, it was also proven that the resin composition according to theembodiment of the present invention is superior in long-run workabilityin melt molding.

INDUSTRIAL APPLICABILITY

The resin composition according to the embodiment of the presentinvention enables occurrences of defects such as fish eyes in meltmolding to be suppressed; therefore, appearance characteristics of themolded articles formed therefrom can be also superior. Also, the resincomposition is less likely to cause the defects even if melt molding iscarried out for a long time period in particular, and also superiorlong-run workability is attained. Therefore, the resin composition issuitably used as various types of packaging materials by molding to formcontainers, films, sheets and the like.

The invention claimed is:
 1. A resin composition, comprising: (A) anethylene-vinyl alcohol copolymer; and (B) an unsaturated aldehyde,wherein a content of the unsaturated aldehyde (B) with respect to theresin composition comprising the ethylene-vinyl alcohol copolymer is0.01 ppm or more and 100 ppm or less.
 2. The resin composition accordingto claim 1, wherein the unsaturated aldehyde (B) is (B-1) an unsaturatedaliphatic aldehyde.
 3. The resin composition according to claim 2,wherein the unsaturated aldehyde (B) is crotonaldehyde, 2,4-hexadienal,2,4,6-octatrienal or a combination thereof.
 4. The resin compositionaccording to claim 1, further comprising a conjugated polyene compound,wherein a content of the conjugated polyene compound is 0.01 ppm or moreand 1,000 ppm or less.
 5. The resin composition according to claim 4,wherein the conjugated polyene compound is sorbic acid, a sorbic acidsalt or a combination thereof, wherein the resin composition furthercomprises 100 ppm or more and 5,000 ppm or less of a boron compound. 6.The resin composition according to claim 1, further comprising aceticacid, an acetic acid salt, or both, wherein a content of acetic acid andthe acetic acid salt is 50 ppm or more and 1,000 ppm or less.
 7. Theresin composition according to claim 1, further comprising a phosphoruscompound, wherein a content of the phosphorus compound is 1 ppm or moreand 200 ppm or less.
 8. A multilayered structure comprising at least oneor more layers each constituted with the resin composition according toclaim 1.